Article having nano-scaled structures and a process for making such article

ABSTRACT

A process for producing an article having modified optical, chemical, and/or physical properties is disclosed. The process includes (a) fluidizing a starting material; (b) forcing the fluidized starting material toward the article; and (c) passing the fluidized starting material through a high energy zone. The passing step can occur before the forcing step; after the forcing step but before the fluidizing material comes in contact with the surface of the article; and/or after the forcing step and after the fluidized material comes in contact with the surface of the article. The properties of the article are modified because the article has nano-scaled structures distributed on the surface of the article and/or at least partially embedded in the article.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application claims the benefit of U.S. ProvisionalApplication No. 60/397,486 filed on Jul. 19, 2002, and U.S. applicationSer. No. 10/623,401 filed on Jul. 18, 2003, both of which applicationsare herein incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to methods for producing articles thatexhibit modified optical, mechanical, and chemical properties;especially methods for producing glass articles containing nano-scaledstructures that exhibit modified properties.

BACKGROUND OF THE INVENTION

An article like glass is used for many purposes in today's society. Forexample, glass articles are used in automotive applications,architectural applications, aerospace applications, etc. Depending onthe application, the glass article will need to have differentproperties. The following are just few examples of the many propertiesof glass articles: color, transmittance, reflectance, luminescence, bulkor surface electric conductivity, UV/IR absorption, hardness, catalytic(including photocatalytic) surface quality, thermal insulation,photochromic behavior, etc.

One way to obtain a glass article having certain properties is to createa new glass composition. For example, transition metal oxides andmetallic colloids have been used to make different glass compositions.The disadvantages of using new glass compositions to achieve differentproperties are the length of time it takes to change the batchcomposition in the furnace, the amount of waste generated as a result ofchanging the batch composition in the furnace, etc. Also, changing thecomposition of the batch can result in glass that is harder to meltwhich increases the cost of the production process.

Another way to obtain a glass article having certain properties is toapply a coating composition over the article. Coating compositions forglass articles are well known in the art. Examples of coatingcompositions include chemical vapor deposition (“CVD”) and physicalvapor deposition (“PVD”) coatings. For example, titanium oxide coatings,fluorine doped tin oxide coatings, and indium doped tin oxide coatingscan be applied over glass articles. Several drawbacks are associatedwith applying a coating composition to a glass article to modify itsproperties. Such drawbacks include appearance imperfections (coatedglass can look different at different angles), chemical and mechanicaldurability problems, costs, optical refractive index mismatch, etc.

There is a need for a novel method of modifying the properties ofvarious articles like glass that does not have the disadvantages of theconventional methods. The present invention provides a novel method formodifying the optical, mechanical, and/or chemical properties of anarticle like glass, ceramic or a polymer by including nano-scaledstructures on the surface and/or at least partially embedded in thearticle.

SUMMARY OF THE INVENTION

In a non-limiting embodiment, the present invention is a process forproducing an article comprising:

(a) fluidizing a starting material;

(b) forcing the fluidized starting material toward the article, thearticle having a certain temperature; and

(c) passing the fluidized starting material through a high energy zone,the passing step can occur before the forcing step; after the forcingstep but before the fluidizing material comes in contact with thesurface of the article; and/or after the forcing step and after thefluidized material comes in contact with the surface of the article,whereby the finished article has nano-scaled structures distributed inthe surface of the article and/or at least partially embedded in thearticle.

In another non-limiting embodiment, the present invention is athree-dimensional article comprising nano-scaled structures distributedon the surface of the article and/or at least partially embedded in thearticle.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 shows a glass article with nano-scaled structures analyzed by across-section technique using a JEOL 2000FX transmission electronmicroscope at 200 kV.

DESCRIPTION OF THE INVENTION

All numbers expressing dimensions, physical characteristics, quantitiesof ingredients, reaction conditions, and the like used in thespecification and claims are to be understood as being modified in allinstances by the term “about”. Accordingly, unless indicated to thecontrary, the numerical values set forth in the following specificationand claims may vary depending upon the desired properties sought to beobtained by the present invention. At the very least, and not as anattempt to limit the application of the doctrine of equivalents to thescope of the claims, each numerical parameter should at least beconstrued in light of the number of reported significant digits and byapplying ordinary rounding techniques. Moreover, all ranges disclosedherein are to be understood to encompass any and all subranges subsumedtherein. For example, a stated range of “1 to 10” should be consideredto include any and all subranges between (and inclusive of) the minimumvalue of 1 and the maximum value of 10; that is, all subranges beginningwith a minimum value of 1 or more and ending with a maximum value of 10or less, e.g., 1 to 7.8, 3 to 4.5, 6.3 to 10.

The terms below are defined herein as follows:

“Deposited over” means deposited or provided on but not necessarily insurface contact with. For example, a coating or material “depositedover” an article does not preclude the presence of one or more othercoating films or materials of the same or different composition locatedbetween the deposited coating or material and the article.

“Nano-scaled structure”—a three dimensional object having a size rangingfrom 1 nm to 1000 nm or 1 nm to 500 nm or 1 nm to 100 nm or 1 to 40 nm.

“Opaque” means having a visible light transmittance of 0%.

“Solar control material” refers to a material that affects the solarperformance properties of the glass, e.g., transmittance and/orreflectance of electromagnetic radiation, such as in the visible,ultraviolet (UV), or infrared (IR) regions of the electromagneticspectrum.

“Starting material” refers to a material or mixture of materials thatare capable of forming nano-scaled structures.

“Transparent” means having a transmittance through the article ofgreater than 0% up to 100%.

“Translucent” means allowing electromagnetic energy (e.g., visiblelight) to pass through but diffusing it such that objects on the otherside are not clearly visible.

“Visible light” means electromagnetic energy in the range of 380 nm to760 nm.

The present invention is a method for producing an article havingmodified properties comprising the steps of (a) fluidizing a startingmaterial; (b) forcing the fluidized starting material toward thearticle, the surface of the article having a certain temperature; and(c) passing the fluidized starting material through a high energy zoneeither before or after the material is forced toward the article.

The first step in the present invention comprises fluidizing a startingmaterial. The following are non-limiting examples of suitable startingmaterials: organometallics or solutions thereof for example titaniumisopropoxide, titanium iso-propoxide in ethanol, tetraethylorthosilicate, or tetraethyl orthosilicate in solution; inorganic saltssuch as hydrogen tetrachloroaurate (III) trihydrate, hydrogentetrachlorate (III) trihydrate in water, cobalt nitrate, or cobaltnitrate in ethanol; and metal oxides or suspensions thereof such ascerium oxide, cerium oxide in water, zinc oxide, or zinc oxide inethanol. Further non-limiting examples include:

An aqueous solution comprising noble metal ions. For example, an aqueoussolution containing HAuCl₄.3H₂O, AgNO₃, a copper compound, or mixturesthereof.

A solution containing titanium ion. For example, a solution comprising0.5-25.0 weight percent of titanium tetra-iso-propoxide dissolved in amixture of ethanol. 2,4-pentanedione can be added as a stabilizer.

(1) A solution containing antimony and tin ions. For example, a solutioncomprising monobutyl tin trichloride and antimony trichloride with aSb³⁺/Sn⁴⁺ ratio of 10% which is diluted in ethanol up to 50.0 weightpercent and stirred for 30 minutes at room temperature.

Some of the starting materials include nano-scaled structures which aredispersed in solution. Other starting materials do not includenano-scaled structures.

In a non-limiting embodiment, prior to fluidization, the temperature ofthe starting material can be maintained at a temperature that allowssufficient sublimation or vaporization from a solid or a liquid startingmaterial or at a temperature at which the starting material has asufficiently low viscosity for atomization, for example, aerosolizationof a liquid. In a non-limiting embodiment, the temperature of thestarting material can range from room temperature to the boilingtemperature of an organometallic liquid.

The starting material can be fluidized in any manner known in the art,including but not limited to, atomizing the starting material into anaerosol; evaporating the starting material into a gas phase; sublimingthe starting material into a gas phase, or other similar techniques.

For example, in a non-limiting embodiment, the starting material can beput into a commercially available atomizer such as Model 9306A from TSI,Inc. to make an aerosol. The atomizer is operated in a standard manner.

Depending on the specific application, the following characteristics ofthe aerosol can be varied: aerosol particle size, the aerosol carriergas, average aerosol droplet (a droplet can be a solid, a liquid, or acombination thereof) size, droplet size distribution of the aerosol,density of the aerosol droplets, flux of aerosol droplets and theaerosol volume output.

In a non-limiting embodiment, the density of the fluidized material canbe sufficient for further processing.

Another step in the present invention comprises forcing the fluidizedmaterial toward the surface of the article; the surface of the articlehaving a certain temperature. In a non-limiting embodiment, thefluidized material can be forced by imparting momentum to the fluidizedmaterials using a moving gas stream. For example, compressed air,compressed nitrogen, etc. can be used to force the fluidized materialtoward the surface of the article. In another non-limiting embodiment,the temperature of the moving gas stream can range from room temperatureto 21009F.

A gravitational field, a thermophoretic field, an electrostatic field, amagnetic field or similar can also be used to force the fluidizedmaterial toward the surface of the article.

Another step in the present invention comprises passing the fluidizedmaterial through a high energy zone. The passing step can beaccomplished in a standard manner such as by supplying an additionalforce or pressure. The passing of the fluidized material step can occur(a) before the forcing step: (b) after the forcing step but before thefluidizing material comes in contact with the surface of the article;and/or (c) after the forcing step and after the fluidized material comesin contact with the surface of the article. In the high energy zone, thefluidized material can be excited using heat, electromagnetic radiation,high voltage or similar to cause the fluidized material to losevolatiles, condense, chemically react, decompose, change phase or acombination thereof.

Examples of suitable high energy zones include, but are not limited to,hot wall reactors, chemical vapor particle deposition reactors (“CVPD”),combustion deposition reactors, plasma chambers, laser beams, microwavechambers, etc.

In a non-limiting embodiment, a hot wall reactor can be the high energyzone. The hot wall reactor is essentially a heated chamber. Startingmaterial can be delivered to the hot wall reactor by a spray system suchas a forced aerosol generator. Inside the reactor, the fluidizedmaterial can lose volatiles, condense, chemically react, decompose,change phase or a combination thereof.

Without limiting the invention, the following describes some of thetypical parameters for the operation of the hot wall reactor in thepresent invention. Typically, the temperature inside the hot wallreactor ranges from 409° F. to 2100° F. or 900° F. to 1650° F. or 1100°F. to 1400° F. The pressure inside the reactor can be ambient or can beindependently controlled. The atmosphere inside the reactor can benitrogen, air, or a mixture of 2 to 5 percent by volume hydrogen and 95to 98 percent by volume nitrogen. The residence time (time the materialis in the reactor) in the reactor has to be sufficient to enable therequisite processing in the high energy zone to occur.

In another non-limiting embodiment, a CVPD reactor can be the highenergy zone. The CVPD is essentially a heated chamber. In a CVPDprocess, starting material can be evaporated to gas phase as inconventional chemical vapor deposition system. The gas phase can then beforced through the CVPD reactor, for example, as a result of a pressuregradient. Inside the reactor, the fluidized material can lose volatiles,condense, chemically react, decompose, change phase or a combinationthereof.

Without limiting the invention, the following describes some typicalparameters for CVPD reactor operation in the present invention.Typically, the temperature inside the CVPD can range from 400° F. to2100° F. or 900° F. to 1650° F. or 1100° F. to 1400° F. The pressureinside the reactor can be ambient or can be independently controlled.The atmosphere inside the reactor can be nitrogen, air, or a mixture of2 to 5 percent by volume hydrogen and 95 to 98 percent by volumenitrogen. The residence time in the reactor has to be sufficient toenable the requisite processing in the high energy zone to occur.

In yet another non-limiting embodiment, a combustion deposition reactoris the high energy zone. In a combustion deposition reactor, startingmaterial can be atomized, for example, by an aerosol generator to forman aerosol. The aerosol can be introduced into a flame.

The aerosol can be introduced into the flame at any position. Atdifferent locations along the flame, the temperature of the flame isdifferent, the chemical make-up of the flame is different, and thevelocity of the flame is different.

In the alternative, the aerosol can be mixed in with the gaseousmixture, e.g. air or oxygen or gas, responsible for the flame. Themixture that makes the flame can be a mixture of a combustible materialand an oxidizing material such as air and natural gas, oxygen andnatural gas, or carbon monoxide and oxygen.

The temperature range of the flame typically can range from 212° F. to2900° F. or 400° F. to 23009F. The residence time (time the material isin the flame) has to be sufficient to enable the requisite processing inthe high energy zone to occur.

In another non-limiting embodiment, a plasma chamber can be the highenergy zone. In the plasma chamber, the fluidized material can be forcedthrough a gas discharge, for example an atmospheric or low pressureplasma, and can be energized through collision with electrons or ionsthat constitute the plasma. The plasma can comprise a reactive gas likeoxygen, an inert gas like argon or a mixture of gases.

The pressure in the plasma chamber can range from 10 mtorr to 760 torr.The residence time in the plasma chamber has to be sufficient to enablethe requisite processing in the high energy zone to occur.

For example, the plasma chamber can be a stainless steel chamber inwhich a gaseous phase is excited to form a plasma.

In a further non-limiting embodiment, a laser beam can be the highenergy zone. The fluidized material can pass through the laser beam andabsorb photons. A suitable laser includes, but is not limited to, a CO₂laser with a wavelength of 10,600 nm. See U.S. Pat. No. 6,482,374 whichis hereby incorporated by reference for an example of a suitable laser.

The fluidized material can be forced to the surface of various articles.Suitable articles for the present invention include, but are not limitedto, polymers, ceramics and glass. The article can be glass; especiallywindow glass made by the float process. The glass can be of any type,such as conventional float glass or flat glass, and can be of anycomposition having any optical properties, e.g., any value of visibletransmission, ultraviolet transmission, infrared transmission, and/ortotal solar energy transmission. Examples of suitable glass includeborosilicate glass and soda-lime-silica glass compositions which arewell known in the art. Exemplary glass compositions are disclosed in,but are not limited to, U.S. Pat. Nos. 5,071,796; 5,837,629; 5,688,727;5,545,596; 5,780,372; 5,352,640; and 5,807,417.

Suitable ceramic articles include oxides such as alumina, zirconia, andclay and non-oxides such as silicon carbide and alumina nitride.

Suitable polymers include polymethylmethacrylate, polycarbonate,polyurethane, polyvinylbutyral (PVB) polyethyleneterephthalate (PET), orcopolymers of any monomers for preparing these, or mixtures thereof.

Just before (up to 1 second prior) the fluidized material comes incontact with the surface of the article, the temperature of the surfaceof the article can range from 25° F. to 3000° F. For glass articles, thetemperature typically can range from 700° F. to 2100° F. or 1100° F. to1900° F. or 1500° F. to 1760° F. For polymer articles, the temperaturetypically can range from 25° F. to 600° F. The temperature of thearticle is one of the factors that determine how far the nano-scaledstructures will penetrate into the article.

After the fluidized material comes in physical contact with the surfaceof the article, nano-scaled structures will be present on the surfaceand/or at least partially embedded in the finished article. Thenano-scaled structures can be bonded to the surface of the article bychemical or mechanical bonding. The nano-scaled structures can beincorporated into the body of the article by the convective flow ofglass, diffusion, or other processes if the viscosity of the article issufficiently low.

The process of the present invention can also comprise optional steps.For example, various coatings can be applied on the article at differentpoints in the process. For example, if the article is glass, ananti-reflective coating or a conductive film can be applied to thearticle before or after the fluidized material is forced toward thesurface of the article. As another example, an alcohol based solution oftitanium iso-propoxide can be sprayed on the surface of the articlebefore or after the fluidized material is forced toward the surface ofthe article.

Also, the invention can include steps related to heating and/or coolingthe article. For example, the article can be heated to change thenano-scaled structures or form, for example, bend or laminate, the finalarticle. Processes such as bending or tempering can serve as a highenergy zone as described above. The article can be heated to atemperature to at least partially dissolve the nano-scaled structures orincrease the depth of penetration of the nano-scaled structures in thearticle. Also, the article can be cooled to produce annealed glass as iswell known in the art.

The process of the present invention will result in the formation of athree dimensional article having nano-scaled structures (a) retained onthe surface or partially embedded in the article, (b) at least partiallyembedded in the article, or (c) fully or partially dissolved in thearticle. See FIG. 1 for an example of an article produced according tothe present invention. The nano-scaled structures can be located on thesurface of the article and/or up to 100 micrometers below the surface ofthe article or up to 20 micrometers below the surface of the article.The nano-scaled structures can be distributed in various ways throughoutthe depth of the article. For example, 100 percent of the nano-scaledstructures can be on the surface of the article. The article can includesolid nano-scaled structures and/or dissolved nano-scaled structures.The nano-scaled structures can have the following shapes: spherical,polyhedral like cubic, triangular, pentagonal, diamond shaped, needleshaped, rod shaped, disc shaped etc. The nano-scaled structures can havean aspect ratio of 1:1 to 1:500 or 1:1 to 1:100. The nano-scaledstructures can have a degree and orientation of crystallinity rangingfrom completely amorphous (0 percent crystallinity) to fully orientatedalong one crystal orientation. The nano-scaled structures can be incontact with each other or separated by a distance of from 1 nm to 1000nm

Depending on the type of nano-scaled structures, the orientation of thenano-scaled structures, the degree of embeddedness of the nano-scaledstructures in the article, etc, various properties of articles can bemodified. For example, the reflectivity of the article can beselectively increased or decreased. The hardness of the article can beincreased. The catalytic property of the article can be increased. Thecolor of the article can be changed. The UV/IR penetration of thearticle can be decreased. The surface area of adhesion for the articlecan be increased. The scattering of the article can be increased for usein, for example, a higher quantum efficiency photovoltaic device.

It is envisioned that the process of the present invention will be usedas part of an on-line production system. For example, the process of thepresent invention can be part of a float glass operation where theprocess is performed near the hot end of a conventional float bath. Theinvention is not limited to use with the float process. For example, theinvention can in a vertical draw process.

The process of the invention has several benefits. First, the inventioneliminates costly down-stream process steps because the invention can bepart of an on-line process. Second, the invention has a short changetime because it can be quickly implemented. Third, the inventionproduces a durable article due to the high temperatures utilized.Fourth, the invention allows the degree of agglomeration of thenano-scaled structures to be controlled. Fifth, the invention can becombined with other processes like CVD, spray pyrolysis, and off-linetechniques like PVD processes.

EXAMPLES

The present invention will now be illustrated by the following,non-limiting examples.

The following examples show how suitable starting materials were made.

Examples of Starting Materials

Example 1

5.0 g of titanium iso-propoxide was mixed into a mixture of 7.0 g of2,4-pentanedione and 88.0 g of reagent alcohol while stirring at roomtemperature for 30 minutes.

Example 2

In a solution already prepared in Example 1 with 5 wt % concentration oftitanium iso-propoxide, 0.084 g of anatase titanium dioxide nanocrystals(ST-01, average size 7 nanometer) from Ishihara Sangyo Kaiha in Japanwas added slowly while vigorously stirring at room temperature.

Example 3

In a solution already prepared in Example 1 with 5 wt % concentration oftitanium iso-propoxide, 2.8 g of a solution consisting of 3.0 wt %brookite titanium dioxide nanocrystals in an alcohol solution (NTB-13)from Showa Denko K. K. in Japan was added slowly while vigorouslystirring at room temperature.

Example 4

In a solution already prepared in Example 1 with 5 wt % concentration oftitanium iso-propoxide, 0.05 g of monobutyl tin trichloride was addedslowly while stirring at room temperature.

Example 5

1 g of antimony chloride and 9 g of monobuytl tin trichloride were addedto 90 g of reagent alcohol while stirring at room temperature.

Example 6

0.1 g hydrogen tetrachloroaurate (III) trihydrate (HAuCl4.3H2O) wasdissolved in 100 g of deionized water resulting in a yellowishtransparent solution. The resultant solution was stored in an opaquecontainer until used.

Example 7

500 g of titanium iso-propoxide.

Example 8

500 g of tetraethyl orthosilicate.

Example 9

5 g of tetraethyl orthosilicate (TEOS) was mixed into 95 g of reagentalcohol while stirring.

Example 10

1 g of Altium™ TiNano 40 anatase nanoparticles from Altair NanomaterialsInc. (Reno, Nev.) was dispersed in 99 g of deionized water whilestirring at room temperature. The mixture was ultrasonically agitatedfor 30 minutes.

Example 11

10 g of NanoTek® nanopowdered cerium oxide purchased from NanophaseTechnologies Corporation (Romeoville, Ill.) was dispersed in 90 g ofdeionized water while stirring at room temperature. The mixture wasultrasonically agitated for 30 minutes.

Example 12

A 15 wt. % NanoTek® nanopowdered zinc oxide in reagent alcoholdispersion was purchased from Nanophase Technology Corporation(Romeoville, Ill.). The material was ultrasonically agitated for 2 hoursto deagglomerate the as-received material.

Example 13

5.0 g of cobalt nitrate was dispersed in 95 g of reagent alcohol. Thesolution was stirred at room temperature for 30 minutes andultrasonically treated for 10 minutes.

Example 14

10.0 g of cerium acetate was dispersed in 45 g of reagent alcohol and145 g of deionized water. The solution was stirred at room temperaturefor 30 minutes and ultrasonically treated for 10 minutes.

Example 15

10.0 g of a cerium nitrate was dispersed in 90 g of reagent alcohol. Thesolution was stirred at room temperature for 30 minutes andultrasonically treated for 10 minutes.

Example 16

10 g of alumatrane (N(CH2CH2O)3Al, approx. 10% CY) as made by TALMaterials (Ann Arbor, Mich.) was mixed with 90 g of reagent alcoholwhile stirring.

Example 17

As in example 10, but the material was zirconia nanoparticles from TALMaterials (Ann Arbor, Mich.).

Example 18

While stirring at room temperature, 20 g of 3.0 wt % brookite titaniumdioxide nanocrystals in an alcohol solution (NTB-13) from Showa DenkoK.K. in Japan was added to a solution of 2.4 g titanium isopropoxidemixed with 3.4 g 2,4-pentanedione in 74.2 g of reagent alcohol.

Performance Examples

In the following examples the starting material was atomized to a streamof aerosol using a single jet atomizer (Model 9302A) from TSIIncorporated (St. Paul, Minn.) with a nitrogen gas input pressure ofeither 25 or 40 Psi (corresponding to an output of 6.6 or 9.2 L/min.) Insome cases, multiple generators were used simultaneously to produce alarger output. The atomizing gas could either be nitrogen or compressedair.

The article to be modified was generally heated in the nitrogenatmosphere of a conveyor furnace. The conveyor speed could be variedfrom 1 to 10″/minute. In a few instances glass was preheated in furnace,moved to the benchtop and then modified in air for a specified period oftime.

The combustion burner for combustion modification was a water-cooled,surface mixing combustion burner where the aerosol was introduced intothe combustion space either by being mixed in with the natural gasstream or by being injected through orifices on the burner face.

In Table 1, properties of nano-scaled structures are shown. Thenano-scaled structures were produced in the following manner. Themixtures of examples 1, 5, 9,10,16, and 17 were atomized (6.6 L/min.)with nitrogen and mixed into an oxygen-gas (ratio of 2.3:1) combustionflame in an air atmosphere. Nanoparticles were collected for 1 minuteonto copper grids at the tip of the flame visible to the naked eye.

The nano-structures were analyzed using a Transmission ElectronMicroscope “TEM” (JEOL 2000FX TEM at an accelerating voltage of 200 kV).

Table 2 shows the modified color properties of articles that wereproduced according to the present.

Article 1 was prepared in the following manner: The starting material ofExample 6 was atomized with a nitrogen gas input pressure of 40 Psi. Thestream of aerosol was then forced by a compressed air with a pressure of20 Psi into the hot wall reactor with a length of 17″, whose temperaturewas set at 1300° F. The PPG Starphire® glass article was stationary andits temperature was also set at 1300° F. The forced aerosol sprayprocess lasted for 1 min. Gold nano-scaled structures were deposited onthe surface of colorless PPG Starphire® glass article after passing thehot wall reactor. The finished PPG Starphire® glass article with goldnano-scaled structures was obtained after cooling to room temperature.The color of the said PPG Starphire® glass article with gold nano-scaledstructures was pink.

Article 2 was formed in the following manner: The above said glassarticle with gold nano-scaled structures was also coated with titaniacoatings using the starting material from Example 1. The depositionprocess was as follows. The starting material of Example 1 was atomizedwith a nitrogen gas input pressure of 40 Psi. The stream of aerosol wasthen forced by a compressed air with a pressure of 20 Psi into the hotwall reactor with a length of 17″, whose temperature was set at 1140 °F. The PPG Starphire® glass article with gold nano-scaled structures wasstationary and its temperature was also set at 11 40° F. The forcedaerosol spray process lasted for 1 min. Titania coatings were depositedon the surface of above said PPG Starphire® glass article with goldnano-scaled structures after passing the hot wall reactor. The final PPGStarphire® glass article with gold/titania nano-scaled structures wasobtained after cooling to room temperature. The color of the said PPGStarphire® glass article with gold/titania nano-scaled structures wasblue-green. The gold nano-scaled structures and gold/titania nano-scaledstructures were confirmed by a LEO 1530 scanning electron microscope andits attached energy dispersive spectroscopy, and X-ray diffraction usingPhilips X′Pert MPD X-ray diffractometer from PANalytical (Natick,Mass.).

3 was formed in the following manner: Example 13 was atomized at 19.8L/min. with nitrogen and introduced into an oxygen-gas flame (ratio of4.6:1) which was incident upon Starphire® glass heated to approximately750° C. in a nitrogen atmosphere and moving at 2″/minute through thefurnace. The result was the incorporation of cobalt into the glasssurface. A striking blue color was produced. Transmission was measuredusing a Lamda 9 spectrophotometer produced by Perkin Elmer. The colorwas computed using the L*a*b* system using CIELAB Color (D65, 10°).

Table 3 shows the modified conductivity of articles that were producedaccording to the present invention.

Article 4 was prepared in the following manner: Example 1 was atomizedat 6.6 L/min. with nitrogen, injected into an oxygen-gas flame (ratio of4.6:1) which was incident upon clear glass heated to approximately 550°C. and moving at 4″/minute in a nitrogen atmosphere. After the glasscooled, it was coated with approximately 1800 Å thick tin oxide filmapplied by spray pyrolysis. The resultant sample had a rough, conductivesurface, indicating that the roughness, as exemplified by the hazelevel, did not result in a significant drop in conductivity. Haze wasmeasured by a HazeGardPlus made by BykGardner.

Table 4 shows the modified texture of articles that were producedaccording to the present invention.

Articles 5, 6, 7were prepared in the following manner: Example 9 wasatomized (from 19.8 to 36.8 L/min. with either nitrogen or compressedair and introduced into an oxygen-gas flame (ratio of 6.1:1) which wasincident upon Starphireg glass heated to approximately 650° C. moving ateither 5 or 10″/minute in a nitrogen atmosphere. This resulted in silicananoparticles adherent to the glass surface. Samples were produced withvarying degrees of roughness by varying the atomization output,atomization gas, and conveyor speed.

Article 8 was prepared in the following manner: The starting materialfrom Example 5 was atomized with a nitrogen gas input pressure of 40Psi. The stream of aerosol was then forced by a compressed air with apressure of 40 Psi into the hot wall reactor with a length of 17″, whosetemperature was set at 1260° F. The PPG clear glass article was movingat a speed of 3″/min and its temperature was set at 1260° F. Antimonydoped tin oxide nano-scaled structures were deposited on the surface ofmoving PPG clear glass article after passing the hot wall reactor. Thefinished PPG clear glass article with antimony doped tin oxidenano-scaled structures was obtained after cooling to room temperature.

Article 9 was prepared in the following manner: The starting material ofExample 1 was atomized with a nitrogen gas input pressure of 40 Psi. Thestream of aerosol was then forced by a compressed air with a pressure of60 Psi into the hot wall reactor with a length of 17″, whose temperaturewas set at 1260° F. The PPG clear glass article was moving at a speed of1″/min and its temperature was set at 1260° F. Titania nano-scaledstructures were deposited on the surface of moving PPG clear glassarticle after passing the hot wall reactor. The finished PPG clear glassarticle with titania nano-scaled structures was obtained after coolingto room temperature.

The textured surface was measured using Digital Instruments NanoScopeAtomic Force Microscopy with an image statistical data of RMS.

Table 5 shows the modified reflectance (“anti-glare”) properties ofarticles produced according to the present invention.

Article 10 was prepared in the following manner: The starting materialof Example 8 in a glass container with a temperature of 194° F. wasevaporated to its gas phase by bubbling with compressed nitrogen gas.The gas phase was fed in to a CVPD reactor whose temperature was set at1380° F. The gas phase was forced to move faster inside the CVPD reactorby a compressed air with a pressure of 10 Psi. The gas phase decomposedinside the CVPD reactor to form white species. These white species werethereafter forced by the compressed air through the CVPD reactor andtoward a PPG clear glass article with a size of 4″×4″, whose temperaturewas set at 300° F. Thereafter, the PPG clear glass article with whitespecies was heated to 1380° F. for 30 min. After cooling to roomtemperature, a PPG clear glass article with silica nano-scaledstructures was obtained. The silica nano-scaled structures was observedusing a LEO 1530 scanning electron microscope and a 10 keV acceleratingvoltage.

Anti-glare property is represented by a reduction of surface reflectanceof an object. The reflectance at 659 angle of incidence was measured byWVASE32 Spectroscopic Ellipsometer from J. A. Woollam Co., Inc.(Lincoln, Neb.). In Table 5, the PPG clear glass article with silicanano-scaled structures in this invention has only half of integratedreflectance at 659 angle of incidence in comparison to PPG clear glassarticle without silica nano-scaled structures.

Table 6 shows the modified UV properties of articles that were producedaccording to the present invention.

Article 11 was prepared in the following manner: Example 15 was atomized(19.8 L/min.) with nitrogen and introduced into a oxygen-gas flame(ratio of 4.6:1) which was incident upon glass heated to 800° C.,resulting in the incorporation of cerium into the glass surface. X-rayfluorescence showed approximately 4 wt % Ce incorporated into the glass.A decrease in the UV transmission was noted, with minimal change in thevisible and IR portions of the spectrum. Transmission was measured usinga Lamda 9 spectrophotometer produced by Perkin Elmer.

Table 7 shows the modified hydrophilic character of articles that wereproduced according to the present invention.

Article 12 was prepared in the following manner: Example I was atomized(6.6 L/min.) with nitrogen, injected into an oxygen-gas flame (ratio of2.3:1) which was incident upon clear glass at approximately 1800 ° F.for 2 minutes in air. Titanium dioxide nanoparticles were deposited intothe surface region of the hot glass. X-ray diffraction by a PhilipsX'Pert MPD X-ray diffractometer from PANalytical indicated the presenceof rutile titania nanoparticles. Scanning electron microscopy of theglass surface revealed the presence of a many uniformly-sized titaniaparticles less than 50 nm in diameter. The incorporation of the titaniaat the glass surface gave rise to UV-induced hydrophilicity.

Article 13 was prepared in the following manner: Example 18 was atomized(36 L/min.) with nitrogen and pushed toward Starphire® glass heated toapproximately 675° C. in a nitrogen atmosphere. For this sample, therewas no flame; the aerosol was produced and kept to less than 200° F.until it was within 3 inches of the top surface of the article.

Article 14 was prepared in the following manner: The starting materialof Example 1 was atomized with a nitrogen gas input pressure of 40 PSI.The stream of aerosol was then forced by a compressed air with apressure of 60 PSI into the hot wall reactor with a length of 17″, whosetemperature was set at 1260° F. The PPG clear glass article was movingat a speed of 2″/min and its temperature was set at 1260° F. Titanianano-scaled structures were deposited on the surface of moving PPG clearglass article after passing the hot wall reactor. The finished PPG clearglass article with titania nano-scaled structures was obtained aftercooling to room temperature. The titania nano-scaled structures wasconfirmed by a LEO 1530 scanning electron microscope and its attachedenergy dispersive spectroscopy. The anatase titania crystal phase wasdetermined by Philips X'Pert MPD X-ray diffractometer from PANalytical(Natick, Mass.).

UV-induced hydrophilicity was characterized by monitoring the decreaseof water contact angle on the article surface as a function of UVexposure time (UVA is 340 nm at 28 W/m2 or UVC is 254 nm).

Table 8 shows the modified photocatalytic activity of articles that wereproduced according to the present invention.

Article 15 was prepared in the following manner: The starting materialof Example 1 was atomized to a stream of aerosol using a Six-JetAtomizer (Model 9306A) from TSI Incorporated (St. Paul, Minn.) with anitrogen gas input pressure of 40 PSI. The stream of aerosol was thenforced by a compressed air with a pressure of 60 PSI into the hot wallreactor with a length of 17″, whose temperature was set at 1260° F. ThePPG clear glass article was moving at a speed of 2″/min and itstemperature was set at 1260° F. Titania nano-scaled structures weredeposited on the surface of moving PPG clear glass article after passingthe hot wall reactor. The finished PPG clear glass article with titanianano-scaled structures was obtained after cooling to room temperature.The titania nano-scaled structures was confirmed by a LEO 1530 scanningelectron microscope and its attached energy dispersive spectroscopy. Theanatase titania crystal phase was determined by Philips X'Pert MPD X-raydiffractometer from PANalytical (Natick, Mass.).

Photocatalytic activity (PCA) was measured from the articles withtitania nano-scaled structures in this invention towards the degradationof stearic acid by monitoring the decrease of integrated IR absorbancein the —CH2 stretching model as a function of UVA-340 exposure time at28 W/m2. The IR absorbance in the -CH2 stretching model was measuredusing an ATI Mattson Infinity Series FTIR spectroscopy from ThermoMattson (Madison, Wis.). The slope of this plot is designated as thephotocatalytic activity (PCA). As shown in Table 1, the articles withtitania nano-scaled structures in this invention has a new function ofphotocatalytic activity at a level of 71×10-3 cm-1 -min-1 compared toPPG clear glass without titania nano-scaled structures, which has nophotocatalytic property. TABLE 1 Properties of nano-scaled structuresaccording to the Present Invention Particle Size (nm) Material (measuredin TEM) Comments Example 1    10 nm Example 5    20 nm Example 9    20nm Example 16  <20 nm Wide size >500 nm distribution Example 10 <100 nmMany small particles and agglomerates Example 17 >500 nm Agglomerates ofvarious sizes

TABLE 2 Color Properties of Articles of the Present Invention ColorColorless Pink Blue-green Test Specimen Starphire ® glass Article 1Article 2 Thickness (”) 0.1267 0.1267 0.1267 L* 96.58 91.86 81.23 a*−0.13 6.60 −18.96 b* 0.11 −2.10 −8.82 Color Colorless Blue Test SpecimenStarphire ® glass Article 3 Thickness (”) 0.1548 0.1548 L 96.51 81.89 a*−0.17 −1.47 b* 0.1 −20.81

TABLE 3 Conductivity of articles of the Present Invention HazeResistance (Ω) Control 2 99 Article 4 19 86

TABLE 4 Texture of articles of the Present Invention Test Specimen RMS(nm) PPG clear glass control sample 0.33 Article 5 0.95 Article 6 4.2Article 7 11.9 Article 8 16.45 Article 9 15.97

TABLE 5 Reflectance (“Anti-glare”) Properties of Articles of the PresentInvention Test Integrated reflectance at Specimen 65° angle of incidence(%) Article 10 7.24 Control 14.62

TABLE 6 UV Properties of Articles of the Present Invention Change intransmission characteristics for PPG Clear glass (“control”) and Article11 IR Total UV Visible (ASTM Solar (ISO 9050, (ASTM 891, 800- (SAE, 300-280-380 nm) 891, 2°) 2500 nm) 2500 nm) % Δ Transmission −14% −2% −1% −2%(% Δ = (Article 11 − control)/control)

TABLE 7 Hydrophilic Character of Articles of the Present InventionTitania-treated PPG Clear glass glass) Article 12: 26 7 Contact anglewith water after 6 hours of UVA exposure Article 13: 23 2 Contact anglewith water after 12 hours of UVC exposure UVA-340 exposure time (min)PPG clear glass Article 14  0 34 32.7  5 45 28.3 15 40 7.7 25 44 7.7 3543 6.3 45 48 6.7 60 40 5

TABLE 8 Photocatalytic Activity of Articles of the Present Invention PPGclear glass Article 15 PCA (×10⁻³ cm⁻¹ · min⁻¹) 0 71

CONCLUSION

By utilizing the process of the present invention, the followingproperties of the sample articles could be changed: color, conductivity,UV absorption, reflectivity, photocatalytic ability, etc.

It will be readily appreciated by those skilled in the art thatmodifications can be made to the invention without departing from theconcepts disclosed in the foregoing description. Such modifications areto be considered as included within the scope of the invention.Accordingly, the particular embodiments described in detail hereinaboveare illustrative only and are not limiting as to the scope of theinvention, which is to be given the full breadth of the appended claimsand any and all equivalents thereof.

1. A process for producing an article, comprising: fluidizing anorganometallic solution by atomizing the organometallic solution into anaerosol; passing the fluidized material through a high energy zoneselected from the group consisting of a hot wall reactor or a combustionreactor; and forcing the fluidized material toward a glass substrateusing a moving gas stream, the glass substrate having a temperaturebetween 700° F. and 2100° F., wherein a finished article has nano-scaledstructures distributed in a surface of the glass substrate or at leastpartially embedded in the glass substrate.
 2. The process of claim 1,wherein the organometallic solution is selected from organometallicsolutions comprising at least one of titanium iso-propoxide, tetraethylorthosilicate, hydrogen tetrachloroaurate (III) trihydrate, cobaltnitrate, and metal oxides.
 3. The process of claim 2, wherein the metaloxides are selected from oxides of cerium, titanium, zinc, and mixturesthereof.
 4. The process of claim 1, wherein the organometallic solutioncomprises nano-scaled structures.
 5. The process of claim 1, wherein theprocess is an on-line production process. 6-18. (canceled)